Aminoalkoxysilane Reactivity in Surface Amine Gradients Prepared by

Nov 6, 2012 - (CRI). The aminoalkoxysilanes used include those that contain primary, ... promising approach termed “controlled-rate infusion” (CRI...
0 downloads 0 Views 1MB Size
Download PDF
Article pubs.acs.org/Langmuir

Aminoalkoxysilane Reactivity in Surface Amine Gradients Prepared by Controlled-Rate Infusion Balamurali Kannan,† Daniel A. Higgins,*,‡ and Maryanne M. Collinson*,† †

Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284-2006, United States Department of Chemistry, Kansas State University, Manhattan, Kansas 66506, United States

‡

ABSTRACT: The reactivity of a series of substituted aminoalkoxysilanes for surface amine gradient formation has been studied using a newly developed time-based exposure method termed controlled-rate infusion (CRI). The aminoalkoxysilanes used include those that contain primary, secondary, and tertiary monoamines as well as more than one amine group (diamine and triamine). X-ray photoelectron spectroscopy (XPS) was used to confirm the presence of a gradient in each case and to acquire detailed information on gradient composition from which kinetic data were obtained. The total area under the N 1s XPS spectra allows for the extent of amine modification to be quantitatively assessed along each gradient. The N 1s peaks actually appear as doublets, providing additional data on the level of protonation and, hence, amine basicity on the dry surface. The degree of protonation showed an interesting trend toward smaller values running from top to bottom along gradients incorporating the most basic amines. The gradient profiles, including initial steepness and extent of saturation, were shown to be highly dependent on the aminoalkoxysilane precursor employed. The highest levels of modification were achieved for the diamine and primary monoamine precursors while the more hindered amines produced lower levels of surface modification and took longer for saturation to be achieved. By fitting the gradient data to a simple first-order kinetic model, rate constants for the condensation reaction between each aminosilane and accessible surface silanol groups were obtained. The rate constants follow the trend: triamine ∼ diamine > monoamine and primary > secondary > tertiary, indicating kinetic factors also play an important role in controlling surface modification. The presence of more than one amine group on the silane is concluded to enhance the rate of condensation to the surface silanol groups, while the more hindered secondary and tertiary amines slow condensation. Collectively, the results provide valuable new data on how the number of amine groups, degree of substitution, and steric hindrance influence silane reactivity with silica surfaces, amine surface coverage, and basicity along the gradient profile.

■

INTRODUCTION

speed up, slow down, or stop transport of analytes, particles, droplets, and cells along a given direction.14 In recent work from our laboratory, we have developed a promising approach termed “controlled-rate infusion” (CRI) to prepare surface amine gradients with controllable and predictable profiles.14 In initial studies, we used 3-aminopropyltriethoxysilane (APTEOS) to form the gradient and demonstrated its usefulness for creation of stationary phase gradients for planar chromatography.5,14 CRI utilizes a programmable syringe pump to slowly infuse a freshly prepared solution of APTEOS into a reaction chamber containing a vertically oriented substrate. The time-dependent exposure of the hydroxylated substrate to the reactive silane solution forms the chemical gradient.5,14 By changing the concentration of the silane and/or the infusion rate, the shape of the gradient can be changed from shallow to steep with various steps in between, if so desired.14

The fabrication of spatially controlled surface chemical gradients incorporating specific functional groups is an important area in materials chemistry research. These gradient surfaces find numerous applications in diverse fields such as controlled transport and haptotaxis1−3 and separation science.4,5 As discussed in recent reviews,6−8 chemical gradients with a range of functionalities have been prepared by many different techniques. Among those approaches, organosilanebased methods9−12 are very popular and widely used because of the plethora of functionalized silanes that are commercially available, the ease with which these precursors react with hydroxylated surfaces, and the relatively straightforward chemistry involved. Silane-based gradient surfaces have been prepared with a variety of different functional groups including aldehydes, amines, short and long-chain alkanes, semifluorinated hydrocarbons, etc.5,9−17 Many methods for gradient preparation rely on diffusion,9−11 which limits the ability to control the gradient profile (i.e., its shape, steepness, and extent of properties variations). The profile of the gradient is particularly important in applications where it is necessary to © 2012 American Chemical Society

Received: September 5, 2012 Revised: October 26, 2012 Published: November 6, 2012 16091

dx.doi.org/10.1021/la303580c | Langmuir 2012, 28, 16091−16098

Langmuir

Article

Scheme 1. Aminoalkoxysilanes Used in the Study

■

The reactivity of the organoalkoxysilane is also a very important factor in controlling the gradient profile. For CRI to work, the time scale of reactivity between the organosilane and the hydroxylated surface must match the rate of infusion, typically 2−60 min. APTEOS works well because the amine functionality also serves as a catalyst to speed up hydrolysis and condensation. Other aminoalkoxysilanes will react differently, depending on the number of amine groups, degree of substitution, and nature of the alkoxide group. Understanding the nature of these variables will provide the knowledge needed to tailor functionally graded surfaces for chromatography and/ or biological applications. Characterization of the gradient profile, on the other hand, can provide a straightforward approach to evaluate the rate of condensation of an aminosilane to a surface, which is of direct importance to the broad field of surface functionalization and modification. The primary objective of this work was to examine a series of aminoalkoxysilanes having different degrees of substitution (i.e., primary, secondary, and tertiary) and different numbers of amine groups (i.e., monoamines, diamines, triamines) (Scheme 1) to elucidate the most important factors controlling their reactivity with the substrate surface. Gradient surfaces have been prepared from these silanes, characterized with X-ray photoelectron spectroscopy (XPS), and the results fit to a firstorder kinetic model to extract a rate constant for the condensation reaction of the silane with surface OH groups. As shown below, the gradient profile was strongly dependent upon the reactivity of each silane, which was governed by the number of amine groups on the molecule and the degree of amine substitution. Furthermore, a detailed analysis of the N 1s XPS spectra revealed an interesting trend in basicity for the more basic amines, with these surfaces exhibiting a decrease in the level of protonation with increasing amine coverage running from top to bottom along the gradient surface.

EXPERIMENTAL SECTION

Sample Preparation. N-[3-(Trimethoxysilyl)propyl] ethylenediamine (Diamine, 97%) was purchased from Sigma-Aldrich. N-[3(Trimethoxysilyl)propyl] diethylenetriamine (Triamine), n-butylaminopropyltrimethoxysilane (N-Butyl), and N,N-diethylaminopropyltrimethoxysilane (N,N-Diethyl) were purchased from Gelest, Inc. Tetraethoxysilane (TEOS, 98%), dimethyldiethoxysilane (DMDEOS, 97%), and 3-aminopropyltriethoxysilane (APTEOS, 99%) were purchased from Acros Organics. 3-Aminopropyltrimethoxysilane (APTMOS, 97%) was purchased from TCI America. All the silanes were used as received. Silicon wafers (University Wafer, B-doped, ⟨111⟩) were cut to the appropriate size (1 × 2 cm) and then cleaned with fresh concentrated H2SO4:H2O2 (70:30) for 10 min at 70 °C in a water bath (CAUTION: piranha solutions are extremely dangerous and react violently with organic materials). As previously described, the silica sol for the base layer consisted of ethanol, TEOS, DMDEOS, 0.1 M HCl, and water in a 1:0.5:0.15:0.15:0.15 volume ratio and was aged for 24−36 h prior to use.14 This sol was spin-coated on the wafers at 4000 rpm for 30 s and dried in a desiccator overnight. Prior to gradient preparation, the base-layer-coated silicon wafer was soaked in ethanol for 10−12 h for stabilization. Surface amine gradients were prepared by slowly infusing a freshly prepared aminosilane solution into a vial containing the above substrate. The rate of infusion was controlled by use of a programmable syringe pump (NewEra, NE-1000). During infusion, the base-layer-coated substrate was exposed to the aminosilane solution for different amounts of time along its length, thus producing a gradual variation in the level of amine modification from top to bottom. The aminosilane solution used for infusion was prepared by mixing ethanol:silane:water in a 5:0.25:0.05 volume ratio. XPS Characterization. X-ray photoelectron spectroscopy (XPS) analysis was performed with a ThermoFisher ESCAlab 250 imaging Xray photoelectron spectrometer (Al Kα (1486.68 eV)), 500 μm spot size, 50 eV pass energy, 0.1 eV step size). Samples were placed on top of conducting tape on a 5 cm × 2 cm sample holder. XPS spectra were acquired at constant intervals (typically every 1−2 mm) across the wafer and starting ∼1 mm from the edge (line scan). The spectra were calibrated by taking the C 1s peak as 284.6 eV. XPS curve fitting was performed using commercially available software and a Gaussian− 16092

dx.doi.org/10.1021/la303580c | Langmuir 2012, 28, 16091−16098

Langmuir

Article

Lorentzian (70:30) function, after smart background subtraction, similar to published work on amine modified surfaces by Unger et al.18

■

RESULTS AND DISCUSSION Gradient Formation. The process of gradient deposition begins with the formation of a reactive, homogeneous base layer, formed by spin-coating a sol containing TEOS and DMDEOS on a silicon wafer. This substrate provides a uniform layer of silanols to react with the various aminomethoxysilanes.14 The aminosilane solution is infused at constant rate into a vial containing the vertically aligned wafer. Because the bottom of the substrate is exposed to the silane for a longer period of time relative to the top, the surface concentration of the amine groups should decrease from bottom to top. The profile (shape) of the gradient will depend on the concentration of silane in the solution, the rate of infusion, and the rate of condensation of the aminosilane with surface silanol groups (kc). A simplified schematic of the process for forming a gradient is shown in Scheme 2. In this work, the Scheme 2. Simple Schematic of Controlled Rate Infusiona

Figure 1. N 1s spectra acquired along the length of the gradient from top to bottom at ∼1.5 mm intervals for six amine gradients prepared from Triamine, Diamine, N-Butyl, N,N-Diethyl, APTEOS,14 and APTMOS. Infusion solution: ethanol:silane:water volume ratio: 5:0.25:0.05. Infusion time was ∼30 min. The black line corresponds to the spectrum acquired at the very top of the gradient.

aminosilane deposited on the surface relative to either APTEOS or APTMOS, which show similar intensities. The profile (shape) of the different gradients can be best seen by integrating the area under the N 1s peak and plotting it as a function of distance (Figure 2). In this figure, Diamine and Triamine was divided by 2 and 3 to account for the different numbers of associated nitrogen atoms. The nonzero intercept observed in all the profiles has four possible origins:14 the position at which the XPS data was acquired does not exactly

a

The solution containing the aminosilane is slowly infused into a glass vial at a controlled rate. The silane precursor reacts with the hydroxylated surface with a rate constant, kc, as the solution slowly fills the reaction container to form the gradient.

reactivity of a series of aminosilanes was evaluated. All but one (APTEOS) incorporate hydrolyzable methoxy groups, but each differs in the substitution (primary, secondary, tertiary amines) and the number (monoamine, diamine, triamine) of amine groups. By keeping the concentrations and infusion rate constant (or nearly constant), the gradient profile will be determined primarily by kc. Figure 1 shows N 1s spectra acquired at defined intervals along the length of gradient surfaces prepared using Diamine, Triamine, N-Butyl, N,N-Diethyl, and APTMOS. Each plot consists of a total of 12 spectra acquired every ∼1.5 mm along the length of the film. For comparison, APTEOS XPS data from our previous work14 are also shown. As expected, on all six surfaces, the intensity of the N 1s peak increases from top to bottom, confirming the presence of a gradient in nitrogen content and, hence, the level of amine modification. In contrast, control samples prepared by soaking the base-layer-coated substrate in an aminosilane solution showed a uniform concentration of nitrogen across the length of the substrate. The signal intensity was significantly higher for Diamine and Triamine, in part because these precursors have two and three nitrogen atoms, respectively, per molecule. The signal intensity was lowest for the secondary and tertiary amines (N-Butyl and N,N-Diethyl), indicating that a smaller amount of the

Figure 2. N 1s XPS area as a function of distance along the length of the gradient from top (distance = 0 mm) to bottom for gradient films prepared from Diamine (diamonds), Triamine (triangles), N-Butyl (circles), N,N-Diethyl (inverted triangles), and APTMOS (squares). The data for Diamine and Triamine were divided by 2 and 3, respectively. Infusion solution: ethanol:silane:water 5:0.25:0.05 by volume. The solid lines represent fits to the kinetic model described below. 16093

dx.doi.org/10.1021/la303580c | Langmuir 2012, 28, 16091−16098

Langmuir

Article

increases with distance. The highest levels of modification following a 30 min infusion were achieved using the Diamine and APTOMOS precursors while the lowest level of surface modification was observed for the tertiary aminoalkoxysilane. To determine if the observed level of modification reflects a different saturation level for each aminosilane (i.e., a different maximum surface coverage), the base-layer-coated substrates were soaked in the individual aminosilane solutions for 4 h, a time significantly longer than the 30 min infusion time. Results from XPS analysis are given in Table 1. The average N 1s peak

correspond to the top of the gradient; contamination by adventitious nitrogen; vapor phase reactivity of the aminosilanes; and contributions from an initial fast reaction.19,20 The contribution of the first is small relative to the other three but would obviously be higher for a very steep gradient. An estimate of the contribution of adventitious nitrogen can be obtained from negative control samples, which consist of the base-layer-coated silicon wafer. There are some month to month variations, but the N 1s peak area typically ranges from 1100 to 3500 CPS eV. To evaluate vapor phase reactivity, the boiling points of the silanes were compared. All were higher than APTEOS with the exception of APTMOS, which has a boiling point of 92 °C. To evaluate the importance of vapor phase reactivity for APTMOS, the silane solution was infused until the lower half of the substrate was immersed. During infusion, the upper half was then exposed to silane vapor for 15 min. The sample was subsequently rinsed, and the N 1s peak area for the vapor-exposed part of the substrate (e.g., upper half) was determined. The area under the N 1s peak in this region was determined to be 4100 ± 200 CPS eV (N = 3), which is comparable to the negative control N 1s area of 3300 ± 200 CPS eV evaluated on that day, confirming that the reaction occurs predominately in the solution phase. Thus, a significant contribution to the nonzero intercept is concluded to result from an initial fast reaction of the aminosilane with surface silanol groups.14 The reproducibility of the XPS profile and the uniformity of the gradient across its entire width can be seen in Figure 3. In

Table 1. Average N 1s Area for Samples Prepared by Soaking a Base-Layer-Coated Substrate in the Aminosilane Solution (Same Ethanol, Silane, and Water Ratio Used for Gradients in Figure 1) for 4 ha silane a

Diamine Triaminea APTMOS N-Butyl N,N-Diethyl

N 1s area after 4 h soak 16000 12000 20000 16000 14000

± ± ± ± ±

50 300 500 3000 500

N 1s area after 30 min infusionb 18000 13000 18000 12000 10000

± ± ± ± ±

200 400 200 300 300

a

Diamine and Triamine divided by 2 and 3, respectively. bAverage and standard deviation of last three points in Figure 3.

area obtained for the APTMOS, Diamine, and Triamine samples are within 10% of the values obtained at the end of the gradient after a 30 min infusion time, indicating that saturation or near saturation of the surface has been achieved. The maximum surface coverage for the Triamine precursor, however, is significantly smaller than that observed for APTMOS or Diamine. A lower surface coverage in this case could result from steric hindrance due to size differences in the two silanes.21,22 A simple calculation of the cross-sectional area23 yields a surface concentration of ∼7 × 10−10 mol/cm2 for APTMOS as well as ∼5 × 10−10 and ∼4 × 10−10 mol/cm2 for the Diamine and Triamine, respectively. The observed reduction in the N 1s peak area is consistent with the increase in precursor size. It is also possible that because Triamine hydrolyzes and condenses quickly, oligomers could also be present in solution. The relatively large size of these oligomers would hinder their binding to free silanol groups, leading to lower coverage.22 In contrast, for N,N-Diethyl and N-Butyl, the N 1s peak area was 25−30% higher after a 4 h immersion period, indicating that saturation was not achieved in 30 min. In addition to the level of saturation, the gradient profiles for the different silanes differ greatly in their shapes (Figure 2). Gradients prepared under these conditions with Diamine and Triamine have a large positive intercept, are relatively steep at the low amine end, and reach saturation within 7−8 min. In contrast, the N-Butyl and N,N-Diethyl gradients are shallow, and saturation is not observed on the time scale of the experiment (∼30 min). APTMOS falls somewhere in between. The nonzero intercepts are also different for the different aminoalkoxysilanes. Results obtained from APTMOS are similar to that previously described for APTEOS,14 indicating the two precursors have similar reactivity. Reactivity of Aminosilanes and Profile Control. To better understand the origins of the differences in aminosilane reactivity, the kinetics of reactivity with the surface were investigated. Gradients prepared by CRI provide a valuable route to obtain such information, since by design the reaction time increases during gradient formation. By fitting the gradient

Figure 3. N 1s XPS area as a function of distance along the length of the gradient from top to bottom for gradient films prepared from N,NDiethyl and N-Butyl. Infusion solution: ethanol:silane:water 5:0.25:0.05 by volume. The infusion time was ∼30 min. The solid lines represent fits to the kinetic model described below.

this figure, the N 1s line scans were acquired across the width of the N-Butyl and N,N-Diethyl gradients, and the area under the N 1s peak in each case is plotted. In both the plots, the standard deviation is secondary > tertiary amine.33 As can be seen from the data in Table 2, the order of reactivity as evaluated from the gradient profile, follows the same trend: primary > secondary > tertiary amine. What can be concluded is that an increase in alkyl substitution on the amine (secondary and tertiary) group leads to a decrease in the rate and efficiency of cross-linking due to steric crowding in the transition state.33 Another factor that could potentially influence reactivity is the basicity of the amine. In solution, basicity as defined by pKb values is typically primary < secondary > tertiary. For example, the pKb in solution for n-propylamine, an analogue to APTMOS, is 3.47 while di-n-propylamine and tri-n-propylamine, analogues of N-Butyl and N,N-Diethyl, have a pKb of 3.00 and 3.35, respectively.34 Thus, the secondary amine is the strongest base, followed by the tertiary and primary amines (secondary > tertiary > primary). While the analogues of APTMOS and N,N-Diethyl have nearly identical pKb values (differing only by ∼0.1 pKb unit) and thus similar basicities, they have very different reactivities, indicating that basicity is not a determining factor. A similar conclusion was reached by Adachi and Hirano upon examining the effect of amine compounds on the hydrolysis and condensation of vinyltrimethoxysilane-grafted ethylene−propylene copolymer, which was that the reactivity of the amine compounds did not depend on their base dissociation constants.33 Gradient Amine Basicity. In addition to the differences in solution-phase basicity discussed above, the different aminosilanes were also found to yield gradients having different basicities in the dry state. The basicity of the gradient surface and how it changes as a function of position can also be ascertained from the XPS data. The N 1s band in the XPS spectra shown in Figure 1 appears as a doublet with binding energies near 399 and 401 eV. Each spectrum can thus be fitted to two peaks; the lower energy nitrogen peak is from the free amines, and the higher energy peak is due to protonated and Hbonded amines.35,36 Hydrogen-bonding interactions take place between the amine groups and neighboring surface silanol groups; the nitrogen abstracts a proton from a neighboring silanol in an acid−base reaction to yield the protonated

Na(t ) = Ns(0)[1 − exp( −kCsolt )]

where Ns and Na represent the number of accessible reactive surface silanol sites originally present and the number of aminosilane groups on the surface, respectively, while k is the rate constant for the slow surface condensation reaction and Csol the concentration of reactive silica precursors in the sol. The solid lines in Figures 2 and 3 depict the individual fits to the above expression. The values of k obtained from the data shown in Figure 2 are given in Table 2. For comparison, kCsol for APTEOS was found to be 11.8 h−1 in our prior work.14 Table 2. Results from Fit to a Single-Step Kinetic Model gradient

Csol (mM)

Diamine Triamine N-Butyl N,N-Diethyl APTMOS

0.22 0.18 0.19 0.22 0.27

k (mM−1 h−1) 97 91 28 5.5 39

± ± ± ± ±

10 16 7 6.5 9

From Table 2, it can be seen that the reactivity of individual aminosilanes with surface silanol groups on the base-layer coated substrate is strongly dependent on the precursor, with the tertiary amine reacting most slowly and the aminosilanes containing multiple N groups reacting significantly faster. On a 30 min time scale, the Diamine and Triamine gradients reach saturation, whereas the secondary and tertiary gradients do not. Also, the nonzero intercept is slightly larger for the Diamine and Triamine precursors. The order of reactivity follows the trend Diamine ∼ Triamine > APTMOS > N-Butyl > N,NDiethyl. Aminosilanes follow a unique reaction mechanism because of the presence of the basic amine group.24 In particular, hydrolysis and condensation of aminoalkoxysilanes occur rapidly because of the self-catalyzing ability of the basic amine group.24−29 Furthermore, the silane and its hydrolysis and condensation products have excellent water solubility.24 The efficiency at which the aminoalkoxysilane reacts with surface silanol groups can be increased by maximizing hydrolysis and limiting self-condensation.25 This efficiency will depend on a number of factors, most notably the number of amine moieties and whether the amine is sterically and electronically hindered.22,25,27,30 The rate of condensation of APTEOS with surface silanol groups on silica particles with different porosity was previously studied by Okabayashi.19,20 In these studies, kinetic information was obtained for APTEOS in toluene via 29Si CP MAS (crosspolarization and magic-angle spinning) NMR, DRIFT (diffuse reflectance infrared Fourier transform), and/or elemental analysis. The results reported (k ∼ 10−2−10−3 s−1)19,20 are similar to our results for APTMOS, but their experiments were obviously more complex than the ones described herein. In other work, the reaction kinetics of an aminosilane with one 16095

dx.doi.org/10.1021/la303580c | Langmuir 2012, 28, 16091−16098

Langmuir

Article

species.13,35−39 Figure 4 shows curve fitted N 1s spectra obtained near the bottom of the gradient (∼12−13 mm from

Figure 5. Area ratio of the N 1s high energy peak (protonated amine) to low energy peak (free amine) for the different aminosilane precursors. Inset: trend in the area ratio vs distance along the length of the film from top (1 mm) to bottom (16 mm) for four line scans acquired on the gradient film prepared from the N,N-Diethyl precursor.

the length of the gradient from top to bottom. For the gradient films prepared from the N,N-Diethyl silane (Figure 5 inset), the data were very distinct, depicting a clear trend to smaller ratios at the 99.99% confidence level. For N-Butyl, the data demonstrate a similar trend at 94% confidence. It is interesting that the extent of protonation is smaller at the bottom of the gradient compared to the top. The higher packing density at the bottom of the film may make it difficult for the substituted amines to interact with surface silanol groups, thus decreasing the extent of protonation. Changes in hydrogen bonding interactions along the length of the gradient can alter acid/base dissociation constants. The close proximity of the amine groups at the bottom of the gradient will favor intramolecular interactions, in turn altering pKb, and the extent of protonation. Such an effect has been studied before using individual nongradient films in solution prepared by selfassembling carboxylic acid terminated alkanethiols on gold.42,43 The pK values for acid groups in a mixed monolayer, for example, were shown to be slightly smaller than in a pure film, which was attributed to changes in hydrogen bonding interactions and solvation.42,43 This finding demonstrates an appealing characteristic of gradient surfaceshow one single sample can be used to study surface density effects that would otherwise require several nongradient samples to be made and studied one at a time.

Figure 4. N 1s high-resolution XPS spectra curve fitted and deconvoluted into two peaks. Spectra were collected near the bottom of the gradient.

the top of the slide). By comparing the ratio of the two peaks, information can be obtained about the basicity of the surface bound amine groups as a function of surface coverage in a single sample. The area ratio (N1/N2) of the high energy (N1) to low energy (N2) peak varied for the different aminosilanes as shown in Figure 5. Based on the N 1s area ratios, basicity in the dry state follows the trend Diamine ∼ Triamine < APTMOS < N-Butyl < N,NDiethyl, consistent with vapor phase basicity that follows the same trend.40 Choi and co-workers41 recently examined primary, secondary, and tertiary amines on mesoporous silica and looked at the adsorption of CO2 and showed that the adsorption amount and bonding affinity increased with basicity in the same order: primary, secondary, tertiary. The area ratio is lower for the gradients deposited with di- and triamines likely because protonation of consecutive amines in Diamine and Triamine becomes more difficult. XPS results from Metwalli and co-workers on APTEOS, Diamine, and Triamine coated glass support this conclusion.39 For most of the films investigated, the peak area ratio, and hence the surface basicity, were found to be relatively invariant with position along the gradient. Clear exceptions were found for the most basic of the silanes investigated, N,N-Diethyl and the N-Butyl silanes; both show trends to smaller values along

■

CONCLUSIONS The preparation of surface amine gradients with well-defined profiles (shapes) requires a detailed understanding of the reactivity of aminoalkoxysilanes. By understanding factors such as reactivity, basicity, and sterics, it is possible to engineer surface chemical gradients with carefully controlled properties in order to achieve a desired outcome. From a different perspective, gradient surfaces prepared from controlled-rate infusion provide a relatively simple and unique way to evaluate the rate of condensation of silane precursors with surface silanol groups as well as how the chemical properties (e.g., basicity) change as surface density changes. In this work, six aminoalkoxysilanes having different levels of substitution and/or differing numbers of amine groups were chosen for study. The reactivity of the aminosilane with surface silanol groups clearly influenced the gradient profile in terms of both its shape and degree of saturation. Those precursors with more than one amine group reacted and reached saturation more quickly than aminosilane precursors with just one amine 16096

dx.doi.org/10.1021/la303580c | Langmuir 2012, 28, 16091−16098

Langmuir

Article

at the liquid solid interface. J. Colloid Interface Sci. 1987, 119 (1), 203− 210. (12) Lin, Y. S.; Hlady, V. The desorption of ribonuclease A from charge density gradient surface studied by spatially-resolved total internal reflection. Colloids Surf., B 1995, 4, 65−75. (13) Zhang, F.; Sautter, K.; Larsen, A. M.; Findley, D. A.; Davis, R. C.; Samha, H.; Linford, M. R. Chemical vapor deposition of three aminosilanes on silicon dioxide: surface characterization, stability, effects of silane concentration, and cyanine dye adsorption. Langmuir 2010, 26 (18), 14648−14654. (14) Kannan, B.; Dong, D.; Higgins, D. A.; Collinson, M. M. Profile control in surface amine gradients prepared by controlled-rate infusion. Langmuir 2011, 27 (5), 1867−1873. (15) Cui, C. C.; Kirkeminde, A.; Kannan, B.; Collinson, M. M.; Higgins, D. A. Spatiotemporal evolution of fixed and mobile dopant populations in silica thin-film gradients as revealed by single molecule tracking. J. Phys. Chem. C 2011, 115 (3), 728−735. (16) Ye, F. M.; Cui, C. C.; Kirkeminde, A.; Dong, D.; Collinson, M. M.; Higgins, D. A. Fluorescence spectroscopy studies of silica film polarity gradients prepared by infusion-withdrawal dip-coating. Chem. Mater. 2010, 22 (9), 2970−2977. (17) Bhat, R. R.; Fischer, D. A.; Genzer, J. Fabricating planar nanoparticle assemblies with number density gradients. Langmuir 2002, 18 (15), 5640−5643. (18) Graf, N.; Yegen, E.; Gross, T.; Lippitz, A.; Weigel, W.; Krakert, S.; Terfort, A.; Unger, W. E. S. XPS and NEXAFS studies of aliphatic and aromatic amine species on functionalized surfaces. Surf. Sci. 2009, 603 (18), 2849−2860. (19) Shimizu, I.; Yoshino, A.; Okabayashi, H.; Nishio, E.; Oconnor, C. J. Kinetics of interaction of 3-amimopropyltriethoxysilane on a silica gel surface using elemental analysis and diffuse reflectance infrared Fourier transform spectra. J. Chem. Soc., Faraday Trans. 1997, 93 (10), 1971−1979. (20) Yoshino, A.; Okabayashi, H.; Shimizu, I.; Oconnor, C. J. Kinetics of interaction of 3-aminopropyltriethoxysilane with silica gel using elemental analysis and Si-29 NMR spectra. Colloid Polym. Sci. 1997, 275 (7), 672−680. (21) Vasiliev, A. N.; Golovko, L. V.; Trachevsky, V. V.; Hall, G. S.; Khinast, J. G. Adsorption of heavy metal cations by organic ligands grafted on porous materials. Microporous Mesoporous Mater. 2009, 118 (1−3), 251−257. (22) Salon, M. C. B.; Abdelmouleh, M.; Boufi, S.; Belgacem, M. N.; Gandini, A. Silane adsorption onto cellulose fibers: Hydrolysis and condensation reactions. J. Colloid Interface Sci. 2005, 289 (1), 249− 261. (23) Livingston, H. K. Cross sectional areas of molecules adsorbed on solid surfaces. J. Am. Chem. Soc. 1994, 66 (4), 569−573. (24) Beari, F.; Brand, M.; Jenkner, P.; Lehnert, R.; Metternich, H. J.; Monkiewicz, J.; Siesler, H. W. Organofunctional alkoxysilanes in dilute aqueous solution: new accounts on the dynamic structural mutability. J. Organomet. Chem. 2001, 625 (2), 208−216. (25) Paquet, O.; Salon, M. C. B.; Zeno, E.; Belgacem, M. N. Hydrolysis-condensation kinetics of 3-(2-amino-ethylamino)propyltrimethoxysilane. Mater. Sci. Eng., C 2012, 32 (3), 487−493. (26) Pena-Alonso, R.; Rubio, F.; Rubio, J.; Oteo, J. L. Study of the hydrolysis and condensation of gamma-aminopropyltriethoxysilane by FT-IR spectroscopy. J. Mater. Sci. 2007, 42 (2), 595−603. (27) Salon, M. B.; Bardet, M.; Belgacem, M. N. Solvolysis−hydrolysis of N-bearing alkoxysilanes: Reactions studied with 29Si NMR. Silicon Chem. 2008, 3 (6), 335−350. (28) Vandenberg, E. T.; Bertilsson, L.; Liedberg, B.; Uvdal, K.; Erlandsson, R.; Elwing, H.; Lundstrom, I. Structure of 3-aminopropyl triethoxysilane on silicon oxide. J. Colloid Interface Sci. 1991, 147 (1), 103−118. (29) Asenath-Smith, E.; Chen, W. How to prevent the loss of surface functionality derived from aminosilanes. Langmuir 2008, 24 (21), 12405−12409. (30) Salon, M. C. B.; Belgacem, M. N. Competition between hydrolysis and condensation reactions of trialkoxysilanes, as a function

group. Of the monoamine-based silanes, reactivity followed the trend primary > secondary > tertiary. Saturation was not attained for the secondary and tertiary amines during the 30 min infusion time scale at the concentrations used. The results described herein can be explained in terms of steric hindrance resulting from the substitution around the amine group. Apart from the direct applications like cell adhesion studies and chromatographic stationary phases, these amine-functionalized surfaces are ideal surfaces to further modify and build more complex platforms. The amine group can be chemically linked to other reagents (proteins, enzymes, dyes) in solution via simple covalent coupling strategies. The Diamine and Triamine gradients can be used to prepare metal ion gradients that make use of the chelating abilities of these functional groups. Future research will be directed in this fashion.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] (M.M.C.); [email protected] (D.A.H.). Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS We gratefully acknowledge support of this work by the National Science Foundation ((CHE-0647849, CHE0648716) and CHE-0820945 MRI: acquisition of an X-ray photoelectron spectrometer (XPS) for research and education at VCU). We also acknowledge the support of the VCU Nanomaterials Core Characterization (NCC) facility and Dr. Dmitry Pestov for his help with the XPS.

■

REFERENCES

(1) Kim, H.-D.; Peyton, S. R. Bio-inspired materials for parsing matrix physicochemical control of cell migration: A Review. Integr. Biol. 2012, 4 (1), 37−52. (2) Pulsipher, A.; Yousaf, M. N. Surface chemistry and cell biological tools for the analysis of cell adhesion and migration. ChemBioChem 2010, 11 (6), 745−753. (3) Singh, M.; Berkland, C.; Detamore, M. S. Strategies and applications for incorporating physical and chemical signal gradients in tissue engineering. Tissue Eng., Part B 2008, 14 (4), 341−366. (4) Pucci, V.; Raggi, M. A.; Svec, F.; Frechet, J. M. J. Monolithic columns with a gradient of functionalities prepared via photoinitiated grafting for separations using capillary electrochromatography. J. Sep. Sci. 2004, 27 (10−11), 779−788. (5) Kannan, B.; Marin, M. A.; Shrestha, K.; Higgins, D. A.; Collinson, M. M. Continuous stationary phase gradients for planar chromatographic media. J. Chromatogr., A 2011, 1218 (52), 9406−9413. (6) Genzer, J.; Efimenko, K.; Fischer, D. A. Formation mechanisms and properties of semifluorinated molecular gradients on silica surfaces. Langmuir 2006, 22 (20), 8532−8541. (7) Genzer, J.; Bhat, R. R. Surface-bound soft matter gradients. Langmuir 2008, 24 (6), 2294−2317. (8) Ruardy, T. G.; Schakenraad, J. M.; vanderMei, H. C.; Busscher, H. J. Preparation and characterization of chemical gradient surfaces and their application for the study of cellular interaction phenomena. Surf. Sci. Rep. 1997, 29 (1), 3−30. (9) Chaudhury, M. K.; Whitesides, G. M. How to make water run uphill. Science 1992, 256 (5063), 1539−1541. (10) Elwing, H.; Welin, S.; Askendahl, A.; Lundstrom, I. Adsorption of fibrinogen as a measure of the distribution of methyl-groups on silicon surfaces. J. Colloid Interface Sci. 1988, 123 (1), 306−308. (11) Elwing, H.; Welin, S.; Askendal, A.; Nilsson, U.; Lundstrom, I. A wettability gradient-method for studies of macromolecular interactions 16097

dx.doi.org/10.1021/la303580c | Langmuir 2012, 28, 16091−16098

Langmuir

Article

of the amount of water and the nature of the organic group. Colloids Surf., A 2010, 366 (1−3), 147−154. (31) Frei, R.; Blitz, J. P.; Gun’ko, V. M.; Frost, B. E.; Sergeev, V. S. Kinetics and computational studies of an aminosilane reaction with a silsesquioxane silanol. J. Phys. Chem. A 2009, 113 (24), 6612−6619. (32) Salon, M. C. B.; Belgacem, M. N. Hydrolysis-condensation kinetics of different silane coupling agents. Phosphorus, Sulfur Silicon Relat. Elem. 2011, 186 (2), 240−254. (33) Adachi, K.; Hirano, T. Controllable silane water-cross-linking kinetics and curability of ethylene-propylene copolymer by amine compounds. Ind. Eng. Chem. Res. 2008, 47 (6), 1812−1819. (34) Hall, H. K. Correlation of the base strengths of amines. J. Am. Chem. Soc. 1957, 79 (20), 5411−5444. (35) Kallury, K. M. R.; Krull, U. J.; Thompson, M. X-ray photoelectron spectroscopy of silica surfaces treated with polyfunctional silanes. Anal. Chem. 1988, 60 (2), 169−172. (36) Moses, P. R.; Wier, L. M.; Lennox, J. C.; Finklea, H. O.; Lenhard, J. R.; Murray, R. W. X-ray photoelectron-spectroscopy of alkylamine-silanes bound to metal-oxide electrodes. Anal. Chem. 1978, 50 (4), 576−585. (37) Horner, M. R.; Boerio, F. J.; Clearfield, H. M. An XPS investigation of the adsorption of aminosilanes onto metal substrates. J. Adhes. Sci. Technol. 1992, 6 (1), 1−22. (38) Ishida, H.; Chiang, C. H.; Koenig, J. L. The structure of aminofunctional silane coupling agents 1. Gamma-aminopropyltriethoxysilane and its analogs. Polymer 1982, 23 (2), 251−257. (39) Metwalli, E.; Haines, D.; Becker, O.; Conzone, S.; Pantano, C. G. Surface characterizations of mono-, di-, and tri-aminosilane treated glass substrates. J. Colloid Interface Sci. 2006, 298 (2), 825−831. (40) Brauman, J. I.; Riveros, J. M.; Blair, L. K. Gas-phase basicities of amines. J. Am. Chem. Soc. 1971, 93 (16), 3914. (41) Ko, Y. G.; Shin, S. S.; Choi, U. S. Primary, secondary, and tertiary amines for CO2 capture: Designing for mesoporous CO2 adsorbents. J. Colloid Interface Sci. 2011, 361 (2), 594−602. (42) Kim, K.; Kwak, J. Faradaic impedance titration of pure 3mercaptopropionic acid and ethanethiol mixed monolayers on gold. J. Electroanal. Chem. 2001, 512 (1−2), 83−91. (43) Quang, D. V.; Kim, J. K.; Sarawade, P. B.; Tuan, D. H.; Kim, H. T. Preparation of amino-functionalized silica for copper removal from an aqueous solution. J. Ind. Eng. Chem. 2012, 18 (1), 83−87.

16098

dx.doi.org/10.1021/la303580c | Langmuir 2012, 28, 16091−16098